Azametallatranes of Group 14 Elements. Syntheses and X-ray Studies

Syntheses of a series of the title compounds, viz., N(CH2CH2NR)3M−X (1, M = Si, X =
Me, R = SiMe3; 2, M = Si, X = Et, R = SiMe3; 3, M = Si, X = n-Bu, R = SiMe3; 4, M = Si,
X = vinyl, R = SiMe3; 5, M = Si, X = Ph, R = SiMe3; 6, M = Ge, X = Me, R = SiMe3; 7, M
= Ge, X = n-Bu, R = SiMe3; 8, M = Ge, X = Ph, R = SiMe3; 9, M = Sn, X = n-Bu, R =
SiMe3; 10, M = Sn, X = Ph, R = SiMe3; 11, M = Si, X = vinyl, R = Me; 12, M = Ge, X = Me,
R = Me) by the reaction of X−MCl3 with N(CH2CH2NSiMe3Li)3 or with N(CH2CH2NMeLi)3
are reported. Reactions of the novel compounds X−Ge(NMe2)3 (15, X = Ph; 16, X =
1-naphthyl; 17, X = 9-antracenyl; 18, X = 9-phenantrenyl) with N(CH2CH2NHMe)3 or N(CH2CH2NH2)3 resulted in new 1-arylazagermatranes, N(CH2CH2NMe)3Ge−X (19, X = Ph; 20,
X = 1-naphthyl; 21, X = 9-antracenyl; 22, X = 9-phenantrenyl) and N(CH2CH2NH)3Ge−X
(23, X = Ph; 24, X = 1-naphthyl; 25, X = 9-phenantrenyl), respectively. 1-Phenylazagermatrane (23) is transformed to 8 by treatment with n-BuLi/Me3SiCl. Composition and
structures of novel compounds were established by elemental analyses, 1H, 13C, and 29Si
NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly
indicated the presence of a transannular interaction M←Nax for both compounds. quasi-Azametallatranes 5 and 8 possess extremely long M←Nax distances.